1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone refrigerant compositions  and uses thereof

ABSTRACT

The present invention relates to compositions for use in refrigeration and air conditioning systems comprising 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and at least one chlorocarbon, alcohol, ketone, ether, ester, N-(difluoromethyl)-N,N-dimethylamine, 1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane or mixtures thereof, and which are also useful in systems employing a centrifugal compressor The compositions of the present invention may be azeotropic or near azeotropic and are useful in processes for producing refrigeration or heat or as heat transfer fluids.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application is a divisional application of pending application Ser.No. 11/437,051 filed May 19, 2006, which is a divisional of U.S.application Ser. No. 11/062,975 filed Feb. 22, 2005 now U.S. Pat. No.7,094,356 issued Aug. 22, 2006, which claims the priority benefit ofU.S. Provisional Application 60/575,037, filed May 26, 2004, and U.S.Provisional Application 60/584,785, filed Jun. 29, 2004.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions for use in refrigerationand air conditioning systems comprising1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone (PEIK) andat least one chlorocarbon, alcohol, ketone, ether, ester,N-(difluoromethyl)-N,N-dimethylamine,1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane or mixturesthereof. Further, the present invention relates to compositions for usein refrigeration and air-conditioning systems employing a centrifugalcompressor comprising1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone (PEIK) andat least one chlorocarbon, alcohol, ketone, ether, ester,N-(difluoromethyl)-N,N-dimethylamine, perfluoro-N-methylmorpholine,1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane or combinationsthereof. The compositions of the present invention may be azeotropic ornear azeotropic and are useful in processes for producing refrigerationor heat or as heat transfer fluids.

2. Description of Related Art

The refrigeration industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCS) beingphased out as a result of the Montreal Protocol. The solution for mostrefrigerant producers has been the commercialization ofhydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134abeing the most widely used at this time, have zero ozone depletionpotential and thus are not affected by the current regulatory phase outas a result of the Montreal Protocol.

Further environmental regulations may ultimately cause global phase outof certain HFC refrigerants as well. Currently, the automobile industryis facing regulations relating to global warming potential forrefrigerants used in mobile air-conditioning. Therefore, there is agreat current need to identify new refrigerants with reduced globalwarming potential for the automobile air-conditioning market. Should theregulations be more broadly applied in the future, an even greater needwill be felt for refrigerants that can be used in all areas of therefrigeration and air-conditioning industry.

Currently proposed replacement refrigerants for HFC-134a includeHFC-152a, pure hydrocarbons such as butane or propane, or “natural”refrigerants such as CO₂ or ammonia. Many of these suggestedreplacements are toxic, flammable, and/or have low energy efficiency.Therefore, new alternatives are constantly being sought.

The object of the present invention is to provide novel refrigerantcompositions and heat transfer fluids that provide uniquecharacteristics to meet the demands of low or zero ozone depletionpotential and lower global warming potential as compared to currentrefrigerants.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to compositions selected from the groupconsisting of:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-dichloroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    trans-1,2-dichloroethylene;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    N-(difluoromethyl)-N,N-dimethylamine;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    acetone;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    diisopropyl ether;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,2-dimethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    dimethoxymethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-dimethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    tert-butylmethyl ether;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    ethanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    isopropanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    n-propanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    ethyl formate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methyl acetate; and-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methyl formate.

The present invention further relates to the above listed compositionsspecifically for use in refrigeration or air conditioning systemsincluding employing a centrifugal compressor.

The present invention further relates to the above listed compositionsspecifically for use in refrigeration or air conditioning systemsemploying a multistage or 2-stage centrifugal compressor.

The present invention further relates to the above listed compositionsspecifically for use in refrigeration or air conditioning systemsemploying a single pass/single slab heat exchanger.

The present invention further relates to azeotropic or near azeotropicrefrigerant compositions. These compositions are useful in refrigerationor air conditioning systems. The compositions are also useful inrefrigeration or air conditioning systems employing a centrifugalcompressor.

The present invention further relates to processes for producingrefrigeration, heat, and transfer of heat from a heat source to a heatsink using the present inventive compositions.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate the entire contents of all citedreferences in this disclosure. Further, when an amount, concentration,or other value or parameter is given as either a range, preferred range,or a list of upper preferable values and lower preferable values, thisis to be understood as specifically disclosing all ranges formed fromany pair of any upper range limit or preferred value and any lower rangelimit or preferred value, regardless of whether ranges are separatelydisclosed. Where a range of numerical values is recited herein, unlessotherwise stated, the range is intended to include the endpointsthereof, and all integers and fractions within the range. It is notintended that the scope of the invention be limited to the specificvalues recited when defining a range.

The refrigerant compositions of the present invention comprising1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone (PEIK) andat least one chlorocarbon, alcohol, ketone, ether, ester,N-(difluoromethyl)-N,N-dimethylamine,1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane or mixturesthereof. The refrigerant compositions of the present invention maycomprise a mixture of PEIK with combinations of any of the listedcomponents.

The refrigerant compositions of the present invention comprise compoundsselected from chlorocarbons, alcohols, ethers, ketones, esters,N-(difluoromethyl)-N,N-dimethylamine, or1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane. Representativechlorocarbons, alcohols, ethers, ketones, and esters are listed in Table1.

Representative compounds that may be components of the compositions ofthe present invention are listed in Table 1.

TABLE 1 CAS Reg. Compound Chemical Formula Chemical Name No. PEIKCF₃CF₂C(O)CF(CF₃)₂ 1,1,1,2,2,4,5,5,5-nonafluoro-4- 756-13-8(trifluoromethyl)-3-pentanone (or perfluoroethylisopropyl ketone)(CF₃)₃COH Nonafluoro-tert-butanol 2378-02-1  CH₃CHCl₂ 1,1-dichloroethane 75-34-3 t-DCE CHCl═CHCl Trans-1,2-dichloroethylene 156-60-5 (CH₃)₂C═Oacetone  67-64-1 CH₃OC(CH₃)₃ tert-butyl methyl ether 1634-04-4 (CH₃)₂CHOCH(CH₃)₂ diisopropyl ether 108-20-3 CH₃OCH₂CH₂OCH₃1,2-dimethoxyethane 110-71-9 CH₃OCH₂OCH₃ dimethoxymethane 109-87-5(CH₃O)₂CHCH₃ 1,1-dimethoxyethane 534-15-6 CH₃OH methanol  67-56-1CH₃CH₂OH ethanol  64-17-5 CH₃CH₂CH₂OH n-propanol  71-23-8 CH₃CHOHCH₃isopropanol  67-63-0 CH₃COOCH₂CH₃ ethyl acetate 141-78-6 HCOOCH₂CH₃ethyl formate 109-94-4 CH₃COOCH₃ methyl acetate  79-20-9 HCOOCH₃ methylformate 107-31-3 N(CH₃)₂(CHF₂) N-(difluoromethyl)-N,N-dimethylamine683-81-8 CF₃CF₂SCF₂CF₃ 1,1,1,2,2-pentafluoro-2- 155953-22-3  [(pentafluoroethyl)thio]ethane

The compounds listed in Table 1 are available commercially (fromchemical supply houses such as Aldrich, Milwaukee, Wis.) or may beprepared by processes known in the art.1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone (PEIK) iscommercially available from 3M™ (St. Paul, Minn.).

Compositions of the present invention have low or zero ozone depletionpotential and low global warming potential. For example, PEIK and theother compounds of the present invention, alone or in mixtures will haveglobal warming potentials lower than many HFC refrigerants currently inuse.

The compositions of the present invention that are mixtures may beprepared by any convenient method to combine the desired amounts of theindividual components. A preferred method is to weigh the desiredcomponent amounts and thereafter combine the components in anappropriate vessel. Agitation may be used, if desired.

The refrigerant or heat transfer compositions of the present inventioninclude:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    N-(difluoromethyl)-N,N-dimethylamine;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-dichloroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    trans-1,2-dichloroethylene;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    acetone;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    diisopropyl ether;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,2-dimethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    dimethoxymethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-dimethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    ethanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    ethyl formate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    isopropanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methyl acetate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methyl formate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    tert-butylmethyl ether; and-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    n-propanol.

The refrigerant or heat transfer compositions of the present inventionmay be azeotropic or near azeotropic compositions. An azeotropiccomposition is a liquid admixture of two or more substances that has aconstant boiling point that may be above or below the boiling points ofthe individual components. As such an azeotropic composition will notfractionate within the refrigeration or air conditioning system duringoperation, which may reduce efficiency of the system. Additionally, anazeotropic composition will not fractionate upon leakage from therefrigeration or air conditioning system. In the situation where onecomponent of a mixture is flammable, fractionation during leakage couldlead to a flammable composition either within the system or outside ofthe system.

A near azeotropic composition is a substantially constant boiling,liquid admixture of two or more substances that behaves essentially as asingle substance. One way to characterize a near azeotropic compositionis that the vapor produced by partial evaporation or distillation of theliquid has substantially the same composition as the liquid from whichit was evaporated or distilled, that is, the admixture distills/refluxeswithout substantial composition change. Another way to characterize anear azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially the same. Herein, a composition is nearazeotropic if, after 50 weight percent of the composition is removed,such as by evaporation or boiling off, the difference in vapor pressurebetween the original composition and the composition remaining after 50weight percent of the original composition has been removed is less thanabout 10 percent.

The azeotropic refrigerant compositions of the present invention arelisted in Table 2.

TABLE 2 Azeotrope Concentration Azeotrope Component A Component B Wt % AWt % B BP (° C.) PEIK N(CH₃)₂(CHF₂) 70.2 29.8 38.1 PEIK1,1-dichloroethane 78.7 21.3 38.2 PEIK t-DCE 72.0 28.0 31.8 PEIKdiisopropyl ether 85.3 14.7 40.3 PEIK 1,2-dimethoxyethane 92.6 7.4 42.0PEIK dimethoxymethane 79.5 20.5 29.6 PEIK 1,1-dimethoxyethane 85.5 14.544.4 PEIK ethanol 96.8 3.2 44.7 PEIK ethyl formate 82.3 17.7 34.1 PEIKisopropanol 96.7 3.3 45.6 PEIK methanol 97.0 3.0 43.5 PEIK methylacetate 84.4 15.6 35.4 PEIK methyl formate 73.2 26.8 22.6 PEIKtert-butyl methyl ether 83.3 16.7 35.3 PEIK n-propanol 98.4 1.6 47.6

The near azeotropic refrigerant compositions and concentration ranges ofthe present invention are listed in Table 3.

TABLE 3 Near Azeotropic Concentration Range Compounds (A/B) wt % A/wt %B PEIK/N(CH₃)₂(CHF₂) 43-91/57-9 PEIK/CF₃CF₂SCF₂CF₃  1-99/99-1PEIK/1,1-dichloroethane 55-91/45-9 PEIK/t-DCE  48-87/52-12 PEIK/acetone 1-99/99-1 PEIK/diisopropyl ether 63-94/37-6 PEIK/1,2-dimethoxyethane73-96/27-4 PEIK/dimethoxymethane 60-92/40-8 PEIK/1,1-dimethoxyethane61-99/39-1 PEIK/ethanol 87-99/13-1 PEIK/ethyl formate 61-92/39-8PEIK/isopropanol 85-99/15-1 PEIK/methanol 91-99/9-1  PEIK/methyl acetate63-93/37-7 PEIK/methyl formate  53-90/47-10 PEIK/tert-butyl methyl ether63-92/37-8 PEIK/n-propanol 87-99/13-1

The compositions of the present invention may further comprise about0.01 weight percent to about 5 weight percent of a stabilizer, freeradical scavenger or antioxidant. Such additives include but are notlimited to, nitromethane, hindered phenols, hydroxylamines, thiols,phosphites, or lactones. Single additives or combinations may be used.

The compositions of the present invention may further comprise about0.01 weight percent to about 5 weight percent of a water scavenger(drying compound). Such water scavengers may comprise ortho esters suchas trimethyl-, triethyl-, or tripropylortho formate.

The compositions of the present invention may further comprise anultra-violet (UV) dye and optionally a solubilizing agent. The UV dye isa useful component for detecting leaks of the refrigerant composition bypermitting one to observe the fluorescence of the dye in the refrigerantor heat transfer fluid composition at a leak point in or the vicinity ofrefrigeration or air-conditioning apparatus. One may observe thefluorosence of the dye under an ultra-violet light. Solubilizing agentsmay be needed due to poor solubility of such UV dyes in somerefrigerants.

By “ultra-violet” dye is meant a UV fluorescent composition that absorbslight in the ultra-violet or “near” ultra-violet region of theelectromagnetic spectrum. The fluorescence produced by the UVfluorescent dye under illumination by a UV light that emits radiationwith wavelength anywhere from 10 nanometer to 750 nanometer may bedetected. Therefore, if refrigerant containing such a UV fluorescent dyeis leaking from a given point in a refrigeration or air conditioningapparatus, the fluorescence can be detected at the leak point. Such UVfluorescent dyes include but are not limited to naphthalimides,perylenes, coumarins, anthracenes, phenanthracenes, xanthenes,thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives orcombinations thereof.

Solubilizing agents of the present invention comprise at least onecompound selected from the group consisting of hydrocarbons, hydrocarbonethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones,chlorocarbons, esters, lactones, aryl ethers, fluoroethers and1,1,1-trifluoroalkanes.

Hydrocarbon solubilizing agents of the present invention comprisehydrocarbons including straight chained, branched chain or cyclicalkanes or alkenes containing 5 or fewer carbon atoms and only hydrogenwith no other functional groups. Representative hydrocarbon solubilizingagents comprise propane, propylene, cyclopropane, n-butane, isobutane,and n-pentane. It should be noted that if the refrigerant is ahydrocarbon, then the solubilizing agent may not be the samehydrocarbon.

Hydrocarbon ether solubilizing agents of the present invention compriseethers containing only carbon, hydrogen and oxygen, such as dimethylether (DME).

Polyoxyalkylene glycol ether solubilizing agents of the presentinvention are represented by the formula R¹-[(OR²)_(x)OR³]Y, wherein: xis an integer from 1-3; y is an integer from 1-4; R¹ is selected fromhydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atomsand y bonding sites; R² is selected from aliphatic hydrocarbyleneradicals having from 2 to 4 carbon atoms; R³ is selected from hydrogenand aliphatic and alicyclic hydrocarbon radicals having from 1 to 6carbon atoms; at least one of R¹ and R³ is said hydrocarbon radical; andwherein said polyoxyalkylene glycol ethers have a molecular weight offrom about 100 to about 300 atomic mass units. In the presentpolyoxyalkylene glycol ether solubilizing agents represented byR¹-[(OR²)_(x)OR³]_(y): x is preferably 1-2; y is preferably 1; R¹ and R³are preferably independently selected from hydrogen and aliphatichydrocarbon radicals having 1 to 4 carbon atoms; R² is preferablyselected from aliphatic hydrocarbylene radicals having from 2 or 3carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycolether molecular weight is preferably from about 100 to about 250 atomicmass units, most preferably from about 125 to about 250 atomic massunits. The R¹ and R³ hydrocarbon radicals having 1 to 6 carbon atoms maybe linear, branched or cyclic. Representative R¹ and R³ hydrocarbonradicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl,cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the presentpolyoxyalkylene glycol ether solubilizing agents may be incompatiblewith certain compression refrigeration apparatus materials ofconstruction (e.g. Mylar®), R¹ and R³ are preferably aliphatichydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1carbon atom. The R² aliphatic hydrocarbylene radicals having from 2 to 4carbon atoms form repeating oxyalkylene radicals—(OR²)_(x)— that includeoxyethylene radicals, oxypropylene radicals, and oxybutylene radicals.The oxyalkylene radical comprising R² in one polyoxyalkylene glycolether solubilizing agent molecule may be the same, or one molecule maycontain different R² oxyalkylene groups. The present polyoxyalkyleneglycol ether solubilizing agents preferably comprise at least oneoxypropylene radical. Where R¹ is an aliphatic or alicyclic hydrocarbonradical having 1 to 6 carbon atoms and y bonding sites, the radical maybe linear, branched or cyclic. Representative R¹ aliphatic hydrocarbonradicals having two bonding sites include, for example, an ethyleneradical, a propylene radical, a butylene radical, a pentylene radical, ahexylene radical, a cyclopentylene radical and a cyclohexylene radical.Representative R¹ aliphatic hydrocarbon radicals having three or fourbonding sites include residues derived from polyalcohols, such astrimethylolpropane, glycerin, pentaerythritol,1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removingtheir hydroxyl radicals.

Representative polyoxyalkylene glycol ether solubilizing agents includebut are not limited to: CH₃OCH₂CH(CH₃)O(H or CH₃) (propylene glycolmethyl (or dimethyl)ether), CH₃O[CH₂CH(CH₃)O]₂(H or CH₃) (dipropyleneglycol methyl (or dimethyl)ether), CH₃O[CH₂CH(CH₃)O]₃(H or CH₃)(tripropylene glycol methyl (or dimethyl)ether), C₂H₅OCH₂CH(CH₃)O(H orC₂H₅) (propylene glycol ethyl (or diethyl)ether), C₂H₅O[CH₂CH(CH₃)O]₂(Hor C₂H₅) (dipropylene glycol ethyl (or diethyl)ether),C₂H₅O[CH₂CH(CH₃)O]₃(H or C₂H₅) (tripropylene glycol ethyl (ordiethyl)ether), C₃H₇OCH₂CH(CH₃)O(H or C₃H₇) (propylene glycol n-propyl(or di-n-propyl)ether), C₃H₇O[CH₂CH(CH₃)O]₂(H or C₃H₇) (dipropyleneglycol n-propyl (or di-n-propyl)ether), C₃H₇O[CH₂CH(CH₃)O]₃(H or C₃H₇)(tripropylene glycol n-propyl (or di-n-propyl)ether), C₄H₉OCH₂CH(CH₃)OH(propylene glycol n-butyl ether), C₄H₉O[CH₂CH(CH₃)O]₂(H orC₄H₉)(dipropylene glycol n-butyl (or di-n-butyl)ether),C₄H₉O[CH₂CH(CH₃)O]₃(H or C₄H₉) (tripropylene glycol n-butyl (ordi-n-butyl)ether), (CH₃)₃COCH₂CH(CH₃)OH (propylene glycol t-butylether), (CH₃)₃CO[CH₂CH(CH₃)O]₂(H or (CH₃)₃) (dipropylene glycol t-butyl(or di-t-butyl)ether), (CH₃)₃CO[CH₂CH(CH₃)O]₃(H or (CH₃)₃) (tripropyleneglycol t-butyl (or di-t-butyl)ether), C₅H₁₁OCH₂CH(CH₃)OH (propyleneglycol n-pentyl ether), C₄H₉OCH₂CH(C₂H₅)OH (butylene glycol n-butylether), C₄H₉O[CH₂CH(C₂H₅)O]₂H (dibutylene glycol n-butyl ether),trimethylolpropane tri-n-butyl ether (C₂H₅C(CH₂—O—(CH₂)₃CH₃)₃) andtrimethylolpropane di-n-butyl ether (C₂H₅C(CH₂OC(CH₂)₃CH₃)₂CH₂OH).

Amide solubilizing agents of the present invention comprise thoserepresented by the formulae R¹CONR²R³ and cyclo-[R⁴CON(R⁵)—], whereinR¹, R², R³ and R⁵ are independently selected from aliphatic andalicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R⁴ isselected from aliphatic hydrocarbylene radicals having from 3 to 12carbon atoms; and wherein said amides have a molecular weight of fromabout 100 to about 300 atomic mass units. The molecular weight of saidamides is preferably from about 160 to about 250 atomic mass units. R¹,R², R³ and R⁵ may optionally include substituted hydrocarbon radicals,that is, radicals containing non-hydrocarbon substituents selected fromhalogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹,R², R³ and R⁵ may optionally include heteroatom-substituted hydrocarbonradicals, that is, radicals, which contain the atoms nitrogen (aza-),oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed ofcarbon atoms. In general, no more than three non-hydrocarbonsubstituents and heteroatoms, and preferably no more than one, will bepresent for each 10 carbon atoms in R¹⁻³, and the presence of any suchnon-hydrocarbon substituents and heteroatoms must be considered inapplying the aforementioned molecular weight limitations. Preferredamide solubilizing agents consist of carbon, hydrogen, nitrogen andoxygen. Representative R¹, R², R³ and R⁵ aliphatic and alicyclichydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers. A preferredembodiment of amide solubilizing agents are those wherein R⁴ in theaforementioned formula cyclo-[R⁴CON(R⁵)—] may be represented by thehydrocarbylene radical (CR⁶R⁷)_(n), in other words, the formula:cyclo-[(CR⁶R⁷)NCON(R⁵)—] wherein: the previously-stated values formolecular weight apply; n is an integer from 3 to 5; R⁵ is a saturatedhydrocarbon radical containing 1 to 12 carbon atoms; R⁶ and R⁷ areindependently selected (for each n) by the rules previously offereddefining R¹⁻³. In the lactams represented by the formula:cyclo-[(CR⁶R⁷)NCON(R⁵)—], all R⁶ and R⁷ are preferably hydrogen, orcontain a single saturated hydrocarbon radical among the n methyleneunits, and R⁵ is a saturated hydrocarbon radical containing 3 to 12carbon atoms. For example, 1-(saturated hydrocarbonradical)-5-methylpyrrolidin-2-ones.

Representative amide solubilizing agents include but are not limited to:1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one,1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam,1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one,1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam,1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one,1,3-dimethylpiperid-2-one, 1-methylcaprolactam,1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one,1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one,N,N-dibutylformamide and N,N-diisopropylacetamide.

Ketone solubilizing agents of the present invention comprise ketonesrepresented by the formula R¹COR², wherein R¹ and R² are independentlyselected from aliphatic, alicyclic and aryl hydrocarbon radicals havingfrom 1 to 12 carbon atoms, and wherein said ketones have a molecularweight of from about 70 to about 300 atomic mass units. R¹ and R² insaid ketones are preferably independently selected from aliphatic andalicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecularweight of said ketones is preferably from about 100 to 200 atomic massunits. R¹ and R² may together form a hydrocarbylene radical connectedand forming a five, six, or seven-membered ring cyclic ketone, forexample, cyclopentanone, cyclohexanone, and cycloheptanone. R¹ and R²may optionally include substituted hydrocarbon radicals, that is,radicals containing non-hydrocarbon substituents selected from halogens(e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ and R² mayoptionally include heteroatom-substituted hydrocarbon radicals, that is,radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-)or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.In general, no more than three non-hydrocarbon substituents andheteroatoms, and preferably no more than one, will be present for each10 carbon atoms in R¹ and R², and the presence of any suchnon-hydrocarbon substituents and heteroatoms must be considered inapplying the aforementioned molecular weight limitations. RepresentativeR¹ and R² aliphatic, alicyclic and aryl hydrocarbon radicals in thegeneral formula R¹COR² include methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers, as well as phenyl,benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

Representative ketone solubilizing agents include but are not limitedto: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone,cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone,5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone,4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone,2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.

Nitrile solubilizing agents of the present invention comprise nitrilesrepresented by the formula R¹CN, wherein R¹ is selected from aliphatic,alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms,and wherein said nitriles have a molecular weight of from about 90 toabout 200 atomic mass units. R¹ in said nitrile solubilizing agents ispreferably selected from aliphatic and alicyclic hydrocarbon radicalshaving 8 to 10 carbon atoms. The molecular weight of said nitrilesolubilizing agents is preferably from about 120 to about 140 atomicmass units. R¹ may optionally include substituted hydrocarbon radicals,that is, radicals containing non-hydrocarbon substituents selected fromhalogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ mayoptionally include heteroatom-substituted hydrocarbon radicals, that is,radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-)or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.In general, no more than three non-hydrocarbon substituents andheteroatoms, and preferably no more than one, will be present for each10 carbon atoms in R¹, and the presence of any such non-hydrocarbonsubstituents and heteroatoms must be considered in applying theaforementioned molecular weight limitations. Representative R¹aliphatic, alicyclic and aryl hydrocarbon radicals in the generalformula R¹CN include pentyl, isopentyl, neopentyl, tert-pentyl,cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyland their configurational isomers, as well as phenyl, benzyl, cumenyl,mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizingagents include but are not limited to: 1-cyanopentane,2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane,1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanodecane,2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.

Chlorocarbon solubilizing agents of the present invention comprisechlorocarbons represented by the formula RCl_(x), wherein; x is selectedfrom the integers 1 or 2; R is selected from aliphatic and alicyclichydrocarbon radicals having 1 to 12 carbon atoms; and wherein saidchlorocarbons have a molecular weight of from about 100 to about 200atomic mass units. The molecular weight of said chlorocarbonsolubilizing agents is preferably from about 120 to 150 atomic massunits. Representative R aliphatic and alicyclic hydrocarbon radicals inthe general formula RCl_(x) include methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers.

Representative chlorocarbon solubilizing agents include but are notlimited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane,1-chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane,1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.

Ester solubilizing agents of the present invention comprise estersrepresented by the general formula R¹CO₂R², wherein R¹ and R² areindependently selected from linear and cyclic, saturated andunsaturated, alkyl and aryl radicals. Preferred esters consistessentially of the elements C, H and O, have a molecular weight of fromabout 80 to about 550 atomic mass units.

Representative esters include but are not limited to:(CH₃)₂CHCH₂OOC(CH₂)₂₋₄OCOCH₂CH(CH₃)₂ (diisobutyl dibasic ester), ethylhexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate,ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester,dipropyl carbonate, “Exxate 700” (a commercial C₇ alkyl acetate),“Exxate 800” (a commercial C₈ alkyl acetate), dibutyl phthalate, andtert-butyl acetate.

Lactone solubilizing agents of the present invention comprise lactonesrepresented by structures [A], [B], and [C]:

These lactones contain the functional group —CO₂— in a ring of six (A),or preferably five atoms (B), wherein for structures [A] and [B], R₁through R₈ are independently selected from hydrogen or linear, branched,cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. EachR₁ though R₈ may be connected forming a ring with another R₁ through R₈.The lactone may have an exocyclic alkylidene group as in structure [C],wherein R₁ through R₆ are independently selected from hydrogen orlinear, branched, cyclic, bicyclic, saturated and unsaturatedhydrocarbyl radicals. Each R₁ though R₆ may be connected forming a ringwith another R₁ through R₆. The lactone solubilizing agents have amolecular weight range of from about 80 to about 300 atomic mass units,preferred from about 80 to about 200 atomic mass units.Representative lactone solubilizing agents include but are not limitedto the compounds listed in Table 4.

TABLE 4 Molecular Molecular Weight Additive Molecular Structure Formula(amu) (E,Z)-3-ethylidene-5-methyl-dihydro-furan-2-one

C₇H₁₀O₂ 126 (E,Z)-3-propylidene-5-methyl-dihydro-furan-2-one

C₈H₁₂O₂ 140 (E,Z)-3-butylidene-5-methyl-dihydro-furan-2-one

C₉H₁₄O₂ 154 (E,Z)-3-pentylidene-5-methyl-dihydro-furan-2-one

C₁₀H₁₆O₂ 168 (E,Z)-3-Hexylidene-5-methyl-dihydro-furan-2-one

C₁₁H₁₈O₂ 182 (E,Z)-3-Heptylidene-5-methyl-dihydro-furan-2-one

C₁₂H₂₀O₂ 196 (E,Z)-3-octylidene-5-methyl-dihydro-furan-2-one

C₁₃H₂₂O₂ 210 (E,Z)-3-nonylidene-5-methyl-dihydro-furan-2-one

C₁₄H₂₄O₂ 224 (E,Z)-3-decylidene-5-methyl-dihydro-furan-2-one

C₁₅H₂₆O₂ 238(E,Z)-3-(3,5,5-trimethylhexylidene)-5-methyl-dihydrofuran-2-one

C₁₄H₂₄O₂ 224 (E,Z)-3-cyclohexylmethylidene-5-methyl-dihydrofuran-2-one

C₁₂H₁₈O₂ 194 gamma-octalactone

C₈H₁₄O₂ 142 gamma-nonalactone

C₉H₁₆O₂ 156 gamma-decalactone

C₁₀H₁₈O₂ 170 gamma-undecalactone

C₁₁H₂₀O₂ 184 gamma-dodecalactone

C₁₂H₂₂O₂ 198 3-hexyldihydro-furan-2-one

C₁₀H₁₈O₂ 170 3-heptyldihydro-furan-2-one

C₁₁H₂₀O₂ 184 cis-3-ethyl-5-methyl-dihydro-furan-2-one

C₇H₁₂O₂ 128 cis-(3-propyl-5-methyl)-dihydro-furan-2-one

C₈H₁₄O₂ 142 cis-(3-butyl-5-methyl)-dihydro-furan-2-one

C₉H₁₆O₂ 156 cis-(3-pentyl-5-methyl)-dihydro-furan-2-one

C₁₀H₁₈O₂ 170 cis-3-hexyl-5-methyl-dihydro-furan-2-one

C₁₁H₂₀O₂ 184 cis-3-heptyl-5-methyl-dihydro-furan-2-one

C₁₂H₂₂O₂ 198 cis-3-octyl-5-methyl-dihydro-furan-2-one

C₁₃H₂₄O₂ 212 cis-3-(3,5,5-trimethylhexyl)-5-methyl-dihydro-furan-2-one

C₁₄H₂₆O₂ 226 cis-3-cyclohexylmethyl-5-methyl-dihydro-furan-2-one

C₁₂H₂₀O₂ 196 5-methyl-5-hexyl-dihydro-furan-2-one

C₁₁H₂₀O₂ 184 5-methyl-5-octyl-dihydro-furan-2-one

C₁₃H₂₄O₂ 212 Hexahydro-isobenzofuran-1-one

C₈H₁₂O₂ 140 delta-decalactone

C₁₀H₁₈O₂ 170 delta-undecalactone

C₁₁H₂₀O₂ 184 delta-dodecalactone

C₁₂H₂₂O₂ 198 mixture of 4-hexyl-dihydrofuran-2-one and3-hexyl-dihydro-furan-2-one

C₁₀H₁₈O₂ 170

Lactone solubilizing agents generally have a kinematic viscosity of lessthan about 7 centistokes at 40° C. For instance, gamma-undecalactone haskinematic viscosity of 5.4 centistokes andcis-(3-hexyl-5-methyl)dihydrofuran-2-one has viscosity of 4.5centistokes both at 40° C. Lactone solubilizing agents may be availablecommercially or prepared by methods as described in U.S. provisionalpatent application Ser. No. 10/910,495 (inventors being P. J. Fagan andC. J. Brandenburg), filed Aug. 3, 2004, incorporated herein byreference.

Aryl ether solubilizing agents of the present invention further comprisearyl ethers represented by the formula R¹OR², wherein: R¹ is selectedfrom aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² isselected from aliphatic hydrocarbon radicals having from 1 to 4 carbonatoms; and wherein said aryl ethers have a molecular weight of fromabout 100 to about 150 atomic mass units. Representative R¹ arylradicals in the general formula R¹OR² include phenyl, biphenyl, cumenyl,mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R² aliphatichydrocarbon radicals in the general formula R¹OR² include methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.Representative aromatic ether solubilizing agents include but are notlimited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethylphenyl ether and butyl phenyl ether.

Fluoroether solubilizing agents of the present invention comprise thoserepresented by the general formula R¹OCF₂CF₂H, wherein R¹ is selectedfrom aliphatic and alicyclic hydrocarbon radicals having from about 5 toabout 15 carbon atoms, preferably primary, linear, saturated, alkylradicals. Representative fluoroether solubilizing agents include but arenot limited to: C₈H₁₇OCF₂CF₂H and C₆H₁₃OCF₂CF₂H. It should be noted thatif the refrigerant is a fluoroether, then the solubilizing agent may notbe the same fluoroether.

Fluoroether solubilizing agents may further comprise ethers derived fromfluoro-olefins and polyols. The fluoro-olefins may be of the typeCF₂═CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine,fluorine, CF₃ or OR_(f), wherein R_(f) is CF₃, C₂F₅, or C₃F₇.Representative fluoro-olefins are tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinylether. The polyols may be of the type HOCH₂CRR′(CH₂)_(z)(CHOH)_(x)CH₂(CH₂OH)_(y), wherein R and R′ are hydrogen or CH₃ orC₂H₅ and wherein x is an integer from 0-4, y is an integer from 0-3 andz is either zero or 1. Representative polyols are trimethylol propane,pentaerythritol, butane diol, and ethylene glycol.

1,1,1-Trifluoroalkane solubilizing agents of the present inventioncomprise 1,1,1-trifluoroalkanes represented by the general formulaCF₃R¹, wherein R¹ is selected from aliphatic and alicyclic hydrocarbonradicals having from about 5 to about 15 carbon atoms, preferablyprimary, linear, saturated, alkyl radicals. Representative1,1,1-trifluoroalkane solubilizing agents include but are not limitedto: 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

Solubilizing agents of the present invention may be present as a singlecompound, or may be present as a mixture of more than one solubilizingagent. Mixtures of solubilizing agents may contain two solubilizingagents from the same class of compounds, say two lactones, or twosolubilizing agents from two different classes, such as a lactone and apolyoxyalkylene glycol ether.

In the present compositions comprising refrigerant and UV fluorescentdye, from about 0.001 weight percent to about 1.0 weight percent of thecomposition is UV dye, preferably from about 0.005 weight percent toabout 0.5 weight percent, and most preferably from 0.01 weight percentto about 0.25 weight percent.

Solubility of these UV fluorescent dyes in refrigerants may be poor.Therefore, methods for introducing these dyes into the refrigeration orair conditioning apparatus have been awkward, costly and time consuming.U.S. Pat. No. RE 36,951 describes a method, which utilizes a dye powder,solid pellet or slurry of dye that may be inserted into a component ofthe refrigeration or air conditioning apparatus. As refrigerant andlubricant are circulated through the apparatus, the dye is dissolved ordispersed and carried throughout the apparatus. Numerous other methodsfor introducing dye into a refrigeration or air conditioning apparatusare described in the literature.

Ideally, the UV fluorescent dye could be dissolved in the refrigerantitself thereby not requiring any specialized method for introduction tothe refrigeration or air conditioning apparatus. The present inventionrelates to compositions including UV fluorescent dye, which may beintroduced into the system in the refrigerant. The inventivecompositions will allow the storage and transport of dye-containingrefrigerant even at low temperatures while maintaining the dye insolution.

In the present compositions comprising refrigerant, UV fluorescent dyeand solubilizing agent, from about 1 to about 50 weight percent,preferably from about 2 to about 25 weight percent, and most preferablyfrom about 5 to about 15 weight percent of the combined composition issolubilizing agent in the refrigerant. In the compositions of thepresent invention the UV fluorescent dye is present in a concentrationfrom about 0.001 weight percent to about 1.0 weight percent in therefrigerant, preferably from 0.005 weight percent to about 0.5 weightpercent, and most preferably from 0.01 weight percent to about 0.25weight percent.

Optionally, commonly used refrigeration system additives may be added,as desired, to compositions of the present invention in order to enhanceperformance and system stability. These additives are known within thefield of refrigeration, and include, but are not limited to, anti wearagents, extreme pressure lubricants, corrosion and oxidation inhibitors,metal surface deactivators, free radical scavengers, and foam controlagents. In general, these additives are present in the inventivecompositions in small amounts relative to the overall composition.Typically concentrations of from less than about 0.1 weight percent toas much as about 3 weight percent of each additive are used. Theseadditives are selected on the basis of the individual systemrequirements. These additives include members of the triaryl phosphatefamily of EP (extreme pressure) lubricity additives, such as butylatedtriphenyl phosphates (BTPP), or other alkylated triaryl phosphateesters, e.g. Syn-0-Ad 8478 from Akzo Chemicals, tricresyl phosphates andrelated compounds. Additionally, the metal dialkyl dithiophosphates(e.g. zinc dialkyl dithiophosphate (or ZDDP), Lubrizol 1375 and othermembers of this family of chemicals may be used in compositions of thepresent invention. Other antiwear additives include natural product oilsand asymmetrical polyhydroxyl lubrication additives, such as SynergolTMS (International Lubricants). Similarly, stabilizers such as antioxidants, free radical scavengers, and water scavengers may be employed.Compounds in this category can include, but are not limited to,butylated hydroxy toluene (BHT) and epoxides.

Solubilizing agents such as ketones may have an objectionable odor,which can be masked by addition of an odor masking agent or fragrance.Typical examples of odor masking agents or fragrances may includeEvergreen, Fresh Lemon, Chemy, Cinnamon, Peppermint, Floral or OrangePeel, all available commercially, as well as d-limonene and pinene. Suchodor masking agents may be used at concentrations of from about 0.001%to as much as about 15% by weight based on the combined weight of odormasking agent and solubilizing agent.

The present invention further relates to a method of using therefrigerant or heat transfer fluid compositions further comprisingultraviolet fluorescent dye, and optionally, solubilizing agent, inrefrigeration or air conditioning apparatus. The method comprisesintroducing the refrigerant or heat transfer fluid composition into therefrigeration or air conditioning apparatus. This may be done bydissolving the UV fluorescent dye in the refrigerant or heat transferfluid composition in the presence of a solubilizing agent andintroducing the combination into the apparatus. Alternatively, this maybe done by combining solubilizing agent and UV fluorescent dye andintroducing said combination into refrigeration or air conditioningapparatus containing refrigerant and/or heat transfer fluid. Theresulting composition may be used in the refrigeration or airconditioning apparatus.

The present invention further relates to a method of using therefrigerant or heat transfer fluid compositions comprising ultravioletfluorescent dye to detect leaks. The presence of the dye in thecompositions allows for detection of leaking refrigerant in therefrigeration or air conditioning apparatus. Leak detection helps toaddress, resolve or prevent inefficient operation of the apparatus orsystem or equipment failure. Leak detection also helps one containchemicals used in the operation of the apparatus.

The method comprises providing the composition comprising refrigerant,ultra-violet fluorescent dye as described herein, and optionally, asolubilizing agent as described herein, to refrigeration and airconditioning apparatus and employing a suitable means for detecting theUV fluorescent dye-containing refrigerant. Suitable means for detectingthe dye include, but are not limited to, ultra-violet lamp, oftenreferred to as a “black light” or “blue light”. Such ultra-violet lampsare commercially available from numerous sources specifically designedfor this purpose. Once the ultra-violet fluorescent dye containingcomposition has been introduced to the refrigeration or air conditioningapparatus and has been allowed to circulate throughout the system, aleak can be found by shining said ultra-violet lamp on the apparatus andobserving the fluorescence of the dye in the vicinity of any leak point.

The present invention further relates to a method of using thecompositions of the present invention for producing refrigeration orheat, wherein the method comprises producing refrigeration byevaporating said composition in the vicinity of a body to be cooled andthereafter condensing said composition; or producing heat by condensingsaid composition in the vicinity of the body to be heated and thereafterevaporating said composition.

Mechanical refrigeration is primarily an application of thermodynamicswherein a cooling medium, such as a refrigerant, goes through a cycle sothat it can be recovered for reuse. Commonly used cycles includevapor-compression, absorption, steam-jet or steam-ejector, and air.

Vapor-compression refrigeration systems include an evaporator, acompressor, a condenser, and an expansion device. A vapor-compressioncycle re-uses refrigerant in multiple steps producing a cooling effectin one step and a heating effect in a different step. The cycle can bedescribed simply as follows. Liquid refrigerant enters an evaporatorthrough an expansion device, and the liquid refrigerant boils in theevaporator at a low temperature to form a gas and produce cooling. Thelow-pressure gas enters a compressor where the gas is compressed toraise its pressure and temperature. The higher-pressure (compressed)gaseous refrigerant then enters the condenser in which the refrigerantcondenses and discharges its heat to the environment. The refrigerantreturns to the expansion device through which the liquid expands fromthe higher-pressure level in the condenser to the low-pressure level inthe evaporator, thus repeating the cycle.

There are various types of compressors that may be used in refrigerationapplications. Compressors can be generally classified as reciprocating,rotary, jet, centrifugal, scroll, screw or axial-flow, depending on themechanical means to compress the fluid, or as positive-displacement(e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal orjet), depending on how the mechanical elements act on the fluid to becompressed.

Either positive displacement or dynamic compressors may be used in thepresent inventive process. A centrifugal type compressor is thepreferred equipment for the present refrigerant compositions.

A centrifugal compressor uses rotating elements to accelerate therefrigerant radially, and typically includes an impeller and diffuserhoused in a casing. Centrifugal compressors usually take fluid in at animpeller eye, or central inlet of a circulating impeller, and accelerateit radially outward. Some static pressure rise occurs in the impeller,but most of the pressure rise occurs in the diffuser section of thecasing, where velocity is converted to static pressure. Eachimpeller-diffuser set is a stage of the compressor. Centrifugalcompressors are built with from 1 to 12 or more stages, depending on thefinal pressure desired and the volume of refrigerant to be handled.

The pressure ratio, or compression ratio, of a compressor is the ratioof absolute discharge pressure to the absolute inlet pressure. Pressuredelivered by a centrifugal compressor is practically constant over arelatively wide range of capacities.

Positive displacement compressors draw vapor into a chamber, and thechamber decreases in volume to compress the vapor. After beingcompressed, the vapor is forced from the chamber by further decreasingthe volume of the chamber to zero or nearly zero. A positivedisplacement compressor can build up a pressure, which is limited onlyby the volumetric efficiency and the strength of the parts to withstandthe pressure.

Unlike a positive displacement compressor, a centrifugal compressordepends entirely on the centrifugal force of the high-speed impeller tocompress the vapor passing through the impeller. There is no positivedisplacement, but rather what is called dynamic-compression.

The pressure a centrifugal compressor can develop depends on the tipspeed of the impeller. Tip speed is the speed of the impeller measuredat its tip and is related to the diameter of the impeller and itsrevolutions per minute. The capacity of the centrifugal compressor isdetermined by the size of the passages through the impeller. This makesthe size of the compressor more dependent on the pressure required thanthe capacity.

Because of its high-speed operation, a centrifugal compressor isfundamentally a high volume, low-pressure machine. A centrifugalcompressor works best with a low-pressure refrigerant, such astrichlorofluoromethane (CFC-11) or 1,2,2-trichlorotrifluoroethane(CFC-113).

Large centrifugal compressors typically operate at 3000 to 7000revolutions per minute (rpm). Small turbine centrifugal compressors aredesigned for high speeds, from about 40,000 to about 70,000 (rpm), andhave small impeller sizes, typically less than 0.15 meters.

A multi-stage impeller may be used in a centrifugal compressor toimprove compressor efficiency thus requiring less power in use. For atwo-stage system, in operation, the discharge of the first stageimpeller goes to the suction intake of a second impeller. Both impellersmay operate by use of a single shaft (or axle). Each stage can build upa compression ratio of about 4 to 1; that is, the absolute dischargepressure can be four times the absolute suction pressure. An example ofa two-stage centrifugal compressor system, in this case for automotiveapplications, is described in U.S. Pat. No. 5,065,990, incorporatedherein by reference.

The compositions of the present invention suitable for use in arefrigeration or air conditioning systems employing a centrifugalcompressor comprise at least one of:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    N-(difluoromethyl)-N,N-dimethylamine;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-dichloroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    trans-1,2-dichloroethylene;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    acetone;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    diisopropyl ether;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,2-dimethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    dimethoxymethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-dimethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    ethanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    ethyl formate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    isopropanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methyl acetate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methyl formate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    tert-butylmethyl ether; or-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    n-propanol.

These above-listed compositions are also suitable for use in amulti-stage centrifugal compressor, preferably a two-stage centrifugalcompressor apparatus.

The compositions of the present invention may be used in stationaryair-conditioning, heat pumps or mobile air-conditioning andrefrigeration systems. Stationary air conditioning and heat pumpapplications include window, ductless, ducted, packaged terminal,chillers and commercial, including packaged rooftop. Refrigerationapplications include domestic or home refrigerators and freezers, icemachines, self-contained coolers and freezers, walk-in coolers andfreezers and transport refrigeration systems.

The compositions of the present invention may additionally be used inair-conditioning, heating and refrigeration systems that employ fin andtube heat exchangers, microchannel heat exchangers and vertical orhorizontal single pass tube or plate type heat exchangers.

Conventional microchannel heat exchangers may not be ideal for the lowpressure refrigerant compositions of the present invention. The lowoperating pressure and density result in high flow velocities and highfrictional losses in all components. In these cases, the evaporatordesign may be modified. Rather than several microchannel slabs connectedin series (with respect to the refrigerant path) a single slab/singlepass heat exchanger arrangement may be used. Therefore, a preferred heatexchanger for the low pressure refrigerants of the present invention isa single slab/single pass heat exchanger.

In addition to two-stage compressor systems, the following compositionsof the present invention are suitable for use in refrigeration or airconditioning systems employing a single slab/single pass heat exchanger:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    N-(difluoromethyl)-N,N-dimethylamine;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-dichloroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    trans-1,2-dichloroethylene;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    acetone;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    diisopropyl ether;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,2-dimethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    dimethoxymethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-dimethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    ethanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    ethyl formate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    n-heptane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    isopropanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methanol;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methyl acetate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    methyl formate;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    tert-butylmethyl ether; and-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    n-propanol.

The compositions of the present invention are particularly useful insmall turbine centrifugal compressors, which can be used in auto andwindow air conditioning or heat pumps as well as other applications.These high efficiency miniature centrifugal compressors may be driven byan electric motor and can therefore be operated independently of theengine speed. A constant compressor speed allows the system to provide arelatively constant cooling capacity at all engine speeds. This providesan opportunity for efficiency improvements especially at higher enginespeeds as compared to a conventional R-134a automobile air-conditioningsystem. When the cycling operation of conventional systems at highdriving speeds is taken into account, the advantage of these lowpressure systems becomes even greater.

Some of the low pressure refrigerant fluids of the present invention maybe suitable as drop-in replacements for CFC-113 in existing centrifugalequipment.

The present invention relates to a process for producing refrigerationcomprising evaporating the compositions of the present invention in thevicinity of a body to be cooled, and thereafter condensing saidcompositions.

The present invention further relates to a process for producing heatcomprising condensing the compositions of the present invention in thevicinity of a body to be heated, and thereafter evaporating saidcompositions.

The present invention further relates to a process for transfer of heatfrom a heat source to a heat sink wherein the compositions of thepresent invention serve as heat transfer fluids. Said process for heattransfer comprises transferring the compositions of the presentinvention from a heat source to a heat sink.

Heat transfer fluids are utilized to transfer, move or remove heat fromone space, location, object or body to a different space, location,object or body by radiation, conduction, or convection. A heat transferfluid may function as a secondary coolant by providing means of transferfor cooling (or heating) from a remote refrigeration (or heating)system. In some systems, the heat transfer fluid may remain in aconstant state throughout the transfer process (i.e., not evaporate orcondense). Alternatively, evaporative cooling processes may utilize heattransfer fluids as well.

A heat source may be defined as any space, location, object or body fromwhich it is desirable to transfer, move or remove heat. Examples of heatsources may be spaces (open or enclosed) requiring refrigeration orcooling, such as refrigerator or freezer cases in a supermarket,building spaces requiring air conditioning, or the passenger compartmentof an automobile requiring air conditioning. A heat sink may be definedas any space, location, object or body capable of absorbing heat. Avapor compression refrigeration system is one example of such a heatsink.

EXAMPLES Example 1 Impact of Vapor Leakage

A vessel is charged with an initial composition at a specifiedtemperature, and the initial vapor pressure of the composition ismeasured. The composition is allowed to leak from the vessel, while thetemperature is held constant, until 50 weight percent of the initialcomposition is removed, at which time the vapor pressure of thecomposition remaining in the vessel is measured. The results aresummarized in Table 5 below.

TABLE 5 After 50% After 50% Compounds Initial Initial Leak Leak Delta wt% A/wt % B Psia kPa Psia kPa P % PEIK/CF₃CF₂SCF₂CF₃ (50.0° C.)  0/10022.71 156.58 22.71 156.58 0.0%  1/99 22.65 156.17 22.64 156.10 0.0%20/80 21.44 147.82 21.16 145.89 1.3% 40/60 20.06 138.31 19.59 135.072.3% 60/40 18.57 128.04 18.04 124.38 2.9% 80/20 16.96 116.94 16.57114.25 2.3% 99/1  15.32 105.63 15.29 105.42 0.2% 100/0  15.23 105.0115.23 105.01 0.0% PEIK/N(CH₃)₂(CHF₂) (38.1° C.) 70.2/29.8 14.68 101.2214.68 101.22 0.0% 90/10 13.76 94.87 12.60 86.87 8.4% 91/9  13.60 93.7712.31 84.87 9.5% 92/8  13.40 92.39 12.01 82.81 10.4% 100/0  9.92 68.409.92 68.40 0.0% 43/57 14.33 98.80 13.00 89.63 9.3% 42/58 14.31 98.6612.80 88.25 10.6%  0/100 10.17 70.12 10.17 70.12 0.0% 54/46 14.54 100.2512.91 89.01 11.2%  0/100 7.47 51.50 7.47 51.50 0.0% PEIK/t-DCE (31.8°C.) 72.0/28.0 14.72 101.49 14.72 101.49 0.0% 85/15 14.62 100.80 14.0396.73 4.0% 87/13 14.56 100.39 13.36 92.11 8.2% 88/12 14.52 100.11 12.8288.39 11.7% 100/0  7.79 53.71 7.79 53.71 0.0% 60/40 14.70 101.35 14.67101.15 0.2% 50/50 14.68 101.22 14.61 100.73 0.5% 48/52 14.68 101.2214.28 98.46 2.7%  0/100 8.34 57.50 8.34 57.50 0.0% PEIK/acetone (50° C.) 0/100 11.85 81.70 11.85 81.70 0.0%  1/99 11.85 81.70 11.85 81.70 0.0%20/80 11.90 82.05 11.90 82.05 0.0% 40/60 12.00 82.74 11.99 82.67 0.1%60/40 12.21 84.19 12.17 83.91 0.3% 80/20 12.76 87.98 12.64 87.15 0.9%99/1  15.02 103.56 14.97 103.22 0.3% 100/0  15.23 105.01 15.23 105.010.0% PEIK/diisopropyl ether (40.3° C.) 85.3/14.7 14.69 101.28 14.69101.28 0.0% 90/10 14.66 101.08 14.53 100.18 0.9% 95/5  14.38 99.15 12.2384.32 15.0% 94/6  14.49 99.91 13.06 90.05 9.9% 100/0  10.77 74.26 10.7774.26 0.0% 63/37 14.58 100.53 13.17 90.8 9.7% 62/38 14.57 100.46 12.6487.15 13.2%  0/100 5.68 39.16 5.68 39.16 0.0% PEIK/1,2-dimethoxyethane(42.0° C.) 92.6/7.4  14.69 101.28 14.69 101.28 0.0% 95/5  14.69 101.2814.69 101.28 0.0% 96/4  14.69 101.28 14.69 101.28 0.0% 100/0  14.4799.77 14.47 99.77 0.0% 80/20 14.69 101.28 14.60 100.66 0.6% 73/27 14.67101.15 13.66 94.18 6.9% 72/28 14.67 101.15 13.06 90.05 11.0%  0/100 3.4323.65 3.43 23.65 0.0% PEIK/dimethoxymethane (29.6° C.) 79.5/20.5 14.72101.49 14.72 101.49 0.0% 90/10 14.71 101.42 14.69 101.28 0.1% 92/8 14.70 101.35 14.69 101.28 0.1% 100/0  7.13 49.16 7.13 49.16 0.0% 60/4014.66 101.08 13.42 92.53 8.5% 59/41 14.65 101.01 13.04 89.91 11.0% 0/100 8.26 56.95 8.26 56.95 0.0% PEIK/1,1-dimethoxyethane (44.4° C.)85.5/14.5 14.67 101.15 14.67 101.15 0.0% 95/5  14.14 97.49 13.76 94.872.7% 99/1  13.02 89.77 12.75 87.91 2.1% 100/0  12.51 86.25 12.51 86.250.0% 60/40 14.10 97.22 12.67 87.36 10.1% 61/39 14.13 97.42 12.89 88.878.8%  0/100 7.49 51.64 7.49 51.64 0.0% PEIK/ethanol (44.7° C.) 96.8/3.2 14.72 101.49 14.72 101.49 0.0% 99/1  14.55 100.32 13.15 90.67 9.6%100/0  12.64 87.15 12.64 87.15 0.0% 87/13 14.59 100.60 13.39 92.32 8.2%86/14 14.57 100.46 12.78 88.12 12.3%  0/100 3.28 22.61 3.28 22.61 0.0%PEIK/ethyl formate (34.1° C.) 82.3/17.7 14.72 101.49 14.72 101.49 0.0%90/10 14.69 101.28 14.41 99.35 1.9% 92/8  14.64 100.94 13.55 93.42 7.4%93/7  14.60 100.66 12.35 85.15 15.4% 100/0  8.52 58.74 8.52 58.74 0.0%60/40 14.70 101.35 12.95 89.29 11.9% 61/39 14.70 101.35 14.66 101.080.3%  0/100 7.11 49.02 7.11 49.02 0.0% PEIK/isopropanol (45.6° C.)96.7/3.3  14.72 101.49 14.72 101.49 0.0% 99/1  14.55 100.32 13.45 92.747.6% 100/0  13.06 90.05 13.06 90.05 0.0% 85/15 14.59 100.60 13.56 93.497.1% 84/16 14.58 100.53 13.10 90.32 10.2%  0/100 2.72 18.75 2.72 18.750.0% PEIK/methanol (43.5° C.) 97.0/3.0  14.72 101.49 14.72 101.49 0.0%99/1  14.51 100.04 13.07 90.12 9.9% 100/0  12.11 83.50 12.11 83.50 0.0%90/10 14.24 98.18 12.62 87.01 11.4% 91/9  14.35 98.94 13.14 90.60 8.4% 0/100 5.77 39.78 5.77 39.78 0.0% PEIK/methyl acetate (35.4° C.)84.4/15.6 14.70 101.35 14.70 101.35 0.0% 90/10 14.69 101.28 14.59 100.600.7% 93/7  14.64 100.94 13.55 93.42 7.4% 94/6  14.60 100.66 11.93 82.2518.3% 100/0  8.96 61.78 8.96 61.78 0.0% 70/30 14.69 101.28 14.67 101.150.1% 63/37 14.68 101.22 14.65 101.01 0.2%  0/100 6.52 44.95 6.52 44.950.0% PEIK/methyl formate (22.6° C.) 73.2/26.8 14.72 101.49 14.72 101.490.0% 90/10 14.70 101.35 13.77 94.94 6.3% 91/9  14.69 101.28 11.87 81.8419.2% 100/0  5.35 36.89 5.35 36.89 0.0% 60/40 14.72 101.49 14.72 101.490.0% 54/46 14.72 101.49 14.71 101.42 0.1% 53/47 14.72 101.49 14.71101.42 0.1%  0/100 9.69 66.81 9.69 66.81 0.0% PEIK/tert-butyl methylether (35.3° C.) 83.3/16.7 14.71 101.42 14.71 101.42 0.0% 90/10 14.71101.42 14.64 100.94 0.5% 92/8  14.69 101.28 14.22 98.04 3.2% 93/7  14.68101.22 12.70 87.56 13.5% 100/0  8.92 61.50 8.92 61.50 0.0% 70/30 14.69101.28 14.52 100.11 1.2% 62/38 14.66 101.08 12.87 88.74 12.2% 63/3714.66 101.08 13.35 92.05 8.9%  0/100 6.70 46.20 6.7 46.20 0.0%PEIK/n-propanol (47.6° C.) 98.4/1.6  14.69 101.28 14.69 101.28 0.0%99/1  14.67 101.15 14.61 100.73 0.4% 100/0  14.01 96.60 14.01 96.60 0.0%86/14 14.48 99.84 12.91 89.01 10.8% 87/13 14.49 99.91 13.42 92.53 7.4% 0/100 1.55 10.69 1.55 10.69 0.0%

The results show the difference in vapor pressure between the originalcomposition and the composition remaining after 50 weight percent hasbeen removed is less then about 10 percent for compositions of thepresent invention. This indicates compositions of the present inventionare azeotropic or azeotrope-like. Where an azeotrope is present, thedata show compositions of the present invention have an initial vaporpressure higher than the vapor pressure of either pure component.

Example 2 Tip Speed to Develop Pressure

Tip speed can be estimated by making some fundamental relationships forrefrigeration equipment that use centrifugal compressors. The torque animpeller ideally imparts to a gas is defined as

T=m*(v ₂ *r ₂ −v ₁ *r ₁)  Equation 1

where

T=torque, N*m

m=mass rate of flow, kg/s

v2=tangential velocity of refrigerant leaving impeller (tip speed), m/s

r₂=radius of exit impeller, m

v₁=tangential velocity of refrigerant entering impeller, m/s

r₁=radius of inlet of impeller, m

Assuming the refrigerant enters the impeller in an essentially radialdirection, the tangential component of the velocity v1=0, therefore

T=m*v ₂ *r ₂  Equation 2

The power required at the shaft is the product of the torque and therotative speed

P=T*w  Equation 3

where

P=power, W

w=rotative speed, rez/s

therefore,

P=T*w=m*v2*r2*w  Equation 4

At low refrigerant flow rates, the tip speed of the impeller and thetangential velocity of the refrigerant are nearly identical; therefore

r ₂ *w=v2  Equation 5

and

P=m*v ₂ *v ₂  Equation 6

Another expression for ideal power is the product of the mass rate offlow and the isentropic work of compression,

P=m*H _(i)*(1000 J/kJ)  Equation 7

where

H_(i)=Difference in enthalpy of the refrigerant from a saturated vaporat the evaporating conditions to saturated condensing conditions, kJ/kg.

Combining the two expressions Equation 6 and 7 produces,

v2*v2=1000*H _(i)  Equation 8

Although Equation 8 is based on some fundamental assumptions, itprovides a good estimate of the tip speed of the impeller and providesan important way to compare tip speeds of refrigerants.

Table 6 below shows theoretical tip speeds that are calculated for1,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the presentinvention. The conditions assumed for this comparison are:

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Liquid subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%These are typical conditions under which small turbine centrifugalcompressors perform.

TABLE 6 Refrigerant Wt % Hi Hi*0.7 Hi*0.7 V2 V2 rel Composition PEIK Wt% B Btu/lb Btu/lb KJ/Kg m/s to CFC-113 CFC-113 100 10.92 7.6 17.8 133.3n/a PEIK plus (B): 1,1-dichloroethane 78.7 21.3 11.41 8.0 18.6 136.3102% t-DCE 72.0 28.0 10.86 7.6 17.7 133.0 100% acetone 50.0 50.0 11.538.1 18.8 137.0 103% diisopropyl ether 85.3 14.6 10.31 7.2 16.8 129.6 97% dimethoxyethane 92.6 7.4 9.65 6.8 15.7 125.3  94% dimethoxymethane79.5 20.5 12.87 9.0 21.0 144.8 109% dimethyl acetal 85.5 14.5 11.08 7.818.0 134.3 101% ethanol 96.8 3.2 10.02 7.0 16.3 127.7  96% ethyl formate82.3 17.7 12.59 8.8 20.5 143.2 107% isopropanol 96.7 3.3 9.59 6.7 15.6125.0  94% methanol 97.0 3.0 10.74 7.5 17.5 132.2  99% methyl acetate84.4 15.6 11.92 8.3 19.4 139.3 105% methyl formate 73.2 26.8 16.72 11.727.2 165.0 124% methy-tert-butyl 83.3 16.7 11.09 7.8 18.1 134.4 101%ether n-propanol 98.4 1.6 9.03 6.3 14.7 121.3  91%

The example shows that compounds of the present invention have tipspeeds within about +/−20 percent of CFC-113 and would be effectivereplacements for CFC-113 with minimal compressor design changes. Mostpreferred compositions have tip speeds within about +/−10 percent ofCFC-113.

Example 3 Performance Data

Table 7 shows the performance of various refrigerants compared toCFC-113. The data are based on the following conditions.

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%

TABLE 7 Evap Evap Cond Cond Compr Compr Refrigerant wt % wt % Pres PresPres Pres Disch Disch Capacity Capacity composition PEIK B (Psia) (kPa)(Psia) (kPa) Temp (F.) Temp (C.) COP (Btu/min) (kW) CFC-113 2.7 19 12.888 156.3 69.1 4.18 14.8 0.26 PEIK plus (B): 1,1-dichloroethane 78.7 21.33.5 24 17.4 120 141.3 60.7 3.97 21.2 0.37 t-DCE 72.0 28.0 4.4 30 21.6149 150.4 65.8 3.99 26.8 0.47 acetone 50.0 50.0 3.6 25 18.4 127 137.158.4 3.94 21.9 0.38 diisopropyl ether 85.3 14.6 3.2 22 16.3 112 127.352.9 3.73 18.1 0.32 dimethoxyethane 92.6 7.4 2.8 19 15.1 104 128.2 53.43.8 16.8 0.29 dimethoxymethane 79.5 20.5 4.5 31 22.7 156 139.0 59.4 3.8626.6 0.47 dimethyl acetal 85.5 14.5 2.7 18 14.1 97 131.9 55.5 3.89 16.30.29 ethanol 96.8 3.2 2.4 17 13.8 95 131.2 55.1 3.87 15.4 0.27 ethylformate 82.3 17.7 3.9 27 19.9 137 140.4 60.2 3.92 23.6 0.41 isopropanol96.7 3.3 2.4 16 13.4 93 129.0 53.9 3.83 14.8 0.26 methanol 97.0 3.0 2.517 14.1 97 135.2 57.3 3.94 16.1 0.28 methyl acetate 84.4 15.6 3.7 2618.8 130 139.6 59.8 3.94 22.5 0.39 methyl formate 73.2 26.8 6.0 41 29.4203 159.2 70.7 3.99 36.5 0.64 methy-tert-butyl 83.3 16.7 3.7 26 18.5 128129.8 54.3 3.76 21.1 0.37 etherData show the compositions of the present invention have evaporator andcondenser pressures similar to CFC-113. Some compositions also havehigher capacity and/or energy efficiency (COP) than CFC-113.

1. A composition selected from the group consisting of:1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and1,1-dichloroethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andN-(difluoromethyl)-N,N-dimethylamine;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andacetone; 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanoneand diisopropyl ether;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and1,2-dimethoxyethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone anddimethoxymethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and1,1-dimethoxyethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andtert-butylmethyl ether;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andethanol; 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanoneand isopropanol;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andn-propanol; 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanoneand ethyl formate;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and methylacetate; and1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and methylformate.
 2. A composition as in claim 1 wherein the composition is arefrigerant or heat transfer fluid composition suitable for use inrefrigeration or air conditioning apparatus employing (i) centrifugalcompressor, or (ii) multi-stage centrifugal compressor, or (iii) asingle slab/single pass heat exchanger, and said composition is selectedfrom the group consisting of:1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and1,1-dichloroethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andN-(difluoromethyl)-N,N-dimethylamine;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andacetone; 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanoneand diisopropyl ether;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and1,2-dimethoxyethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone anddimethoxymethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and1,1-dimethoxyethane;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andtert-butylmethyl ether;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andethanol; 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanoneand isopropanol;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andn-propanol; 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanoneand ethyl formate;1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and methylacetate; and1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and methylformate.
 3. A composition as in claim 1, wherein the composition is anazeotropic or near-azeotropic composition selected from the groupconsisting of: about 55 to about 91 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about45 to about 9 weight percent 1,1-dichloroethane; about 43 to about 91weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about57 to about 9 weight percent N-(difluoromethyl)-N,N-dimethylamine; about1 to about 99 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about99 to about 1 weight percent1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane; about 1 to about99 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about99 to about 1 weight percent acetone; about 63 to about 94 weightpercent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andabout 37 to about 6 weight percent diisopropyl ether; about 73 to about96 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about27 to about 4 weight percent 1,2-dimethoxyethane; about 60 to about 92weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about40 to about 8 weight percent dimethoxymethane; about 61 to about 99weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about39 to about 1 weight percent 1,1-dimethoxyethane; about 63 to about 92weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about37 to about 8 weight percent tert-butyl methyl ether; and about 87 toabout 99 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about13 to about 1 weight percent ethanol; about 85 to about 99 weightpercent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andabout 15 to about 1 weight percent isopropanol; about 87 to about 99weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about13 to about 1 weight percent n-propanol; about 61 to about 92 weightpercent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone andabout 39 to about 8 weight percent ethyl formate; about 63 to about 93weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about37 to about 7 weight percent methyl acetate; and about 53 to about 90weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about47 to about 10 weight percent methyl formate.
 4. A composition as inclaim 1 wherein the composition is an azeotropic composition selectedfrom the group consisting of: 78.7 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 21.3weight percent 1,1-dichloroethane having a vapor pressure of about 14.7psia (101 kPa) at a temperature of about 38.2° C.; 70.2 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 29.8weight percent N-(difluoromethyl)-N,N-dimethylamine having a vaporpressure of about 14.7 psia (101 kPa) at a temperature of about 38.1°C.; 85.3 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 14.7weight percent diisopropyl ether having a vapor pressure of about 14.7psia (101 kPa) at a temperature of about 40.3° C.; 92.6 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 7.4weight percent 1,2-dimethoxyethane having a vapor pressure of about 14.7psia (101 kPa) at a temperature of about 42.0° C.; 79.5 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 20.5weight percent dimethoxymethane having a vapor pressure of about 14.7psia (101 kPa) at a temperature of about 29.6° C.; 85.5 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 14.5weight percent 1,1-dimethoxyethane having a vapor pressure of about 14.7psia (101 kPa) at a temperature of about 44.4° C.; 83.3 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 16.7weight percent tert-butyl methyl ether having a vapor pressure of about14.7 psia (101 kPa) at a temperature of about 35.3° C.; and 96.8 weightpercent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and3.2 weight percent ethanol having a vapor pressure of about 14.7 psia(101 kPa) at a temperature of about 44.7° C.; 96.7 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 3.3weight percent isopropanol having a vapor pressure of about 14.7 psia(101 kPa) at a temperature of about 45.6° C.; 98.4 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1.6weight percent n-propanol having a vapor pressure of about 14.7 psia(101 kPa) at a temperature of about 47.6° C.; 82.3 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 17.7weight percent ethyl formate having a vapor pressure of about 14.7 psia(101 kPa) at a temperature of about 34.1° C.; 84.4 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 15.6weight percent methyl acetate having a vapor pressure of about 14.7 psia(101 kPa) at a temperature of about 35.4° C.; and 73.2 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 26.8weight percent methyl formate having a vapor pressure of about 14.7 psia(101 kPa) at a temperature of about 22.6° C.
 5. A process for producingrefrigeration, said process comprising evaporating the refrigerantcomposition of claim 2, in the vicinity of a body to be cooled, andthereafter condensing said composition.
 6. A process for producing heat,said process comprising condensing the heat transfer composition ofclaim 2 in the vicinity of a body to be heated, and thereafterevaporating said composition.
 7. A process for transferring heat, saidprocess comprising transferring the composition of claim 1 from thevicinity of a heat source to a heat sink.
 8. The composition of claim 1,further comprising at least one ultra-violet fluorescent dye selectedfrom the group consisting of naphthalimides, perylenes, coumarins,anthracenes, phenanthracenes, xanthenes, thioxanthenes,naphthoxanthenes, fluoresceins, derivatives of said dye and combinationsthereof.
 9. The composition of claim 8, further comprising at least onesolubilizing agent selected from the group consisting of hydrocarbons,dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles,chlorocarbons, esters, lactones, aryl ethers, hydrofluoroethers, and1,1,1-trifluoroalkanes; and wherein the refrigerant and solubilizingagent are not the same compound.
 10. The composition of claim 9, whereinsaid solubilizing agent is selected from the group consisting of: a)polyoxyalkylene glycol ethers represented by the formulaR¹[(OR²)_(x)OR³]_(y), wherein: x is an integer from 1 to 3; y is aninteger from 1 to 4; R¹ is selected from hydrogen and aliphatichydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R²is selected from aliphatic hydrocarbylene radicals having from 2 to 4carbon atoms; R³ is selected from hydrogen, and aliphatic and alicyclichydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R¹and R³ is selected from said hydrocarbon radicals; and wherein saidpolyoxyalkylene glycol ethers have a molecular weight of from about 100to about 300 atomic mass units; b) amides represented by the formulaeR¹CONR²R³ and cyclo-[R⁴CON(R⁵)—], wherein R¹, R², R³ and R⁵ areindependently selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms, and at most one aromatic radicalhaving from 6 to 12 carbon atoms; R⁴ is selected from aliphatichydrocarbylene radicals having from 3 to 12 carbon atoms; and whereinsaid amides have a molecular weight of from about 100 to about 300atomic mass units; c) ketones represented by the formula R¹COR², whereinR¹ and R² are independently selected from aliphatic, alicyclic and arylhydrocarbon radicals having from 1 to 12 carbon atoms, and wherein saidketones have a molecular weight of from about 70 to about 300 atomicmass units; d) nitriles represented by the formula R¹CN, wherein R¹ isselected from aliphatic, alicyclic or aryl hydrocarbon radicals havingfrom 5 to 12 carbon atoms, and wherein said nitriles have a molecularweight of from about 90 to about 200 atomic mass units; e) chlorocarbonsrepresented by the formula RCl_(x), wherein; x is selected from theintegers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbonradicals having from 1 to 12 carbon atoms; and wherein saidchlorocarbons have a molecular weight of from about 100 to about 200atomic mass units; f) aryl ethers represented by the formula R¹OR²,wherein: R¹ is selected from aryl hydrocarbon radicals having from 6 to12 carbon atoms; R² is selected from aliphatic hydrocarbon radicalshaving from 1 to 4 carbon atoms; and wherein said aryl ethers have amolecular weight of from about 100 to about 150 atomic mass units; g)1,1,1-trifluoroalkanes represented by the formula CF₃R¹, wherein R¹ isselected from aliphatic and alicyclic hydrocarbon radicals having fromabout 5 to about 15 carbon atoms; i) fluoroethers represented by theformula R¹OCF₂CF₂H, wherein R¹ is selected from aliphatic and alicyclichydrocarbon radicals having from about 5 to about 15 carbon atoms; orwherein said fluoroethers are derived from fluoro-olefins and polyols,wherein said fluoro-olefins are of the type CF₂═CXY, wherein X ishydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃ orOR_(f), wherein R_(f) is CF₃, C₂F₅, or C₃F₇; and said polyols are of thetype HOCH₂CRR′(CH₂)_(z)(CHOH)_(x)CH₂(CH₂OH)_(y), wherein R and R′ arehydrogen, CH₃ or C₂H₅, x is an integer from 0-4, y is an integer from0-3 and z is either zero or 1; and j) lactones represented by structures[B], [C], and [D]:

 wherein, R₁ through R₈ are independently selected from hydrogen,linear, branched, cyclic, bicyclic, saturated and unsaturatedhydrocarbyl radicals; and the molecular weight is from about 100 toabout 300 atomic mass units; and k) esters represented by the generalformula R¹CO₂R², wherein R¹ and R² are independently selected fromlinear and cyclic, saturated and unsaturated, alkyl and aryl radicals;and wherein said esters have a molecular weight of from about 80 toabout 550 atomic mass units.
 11. A process for detecting a leak at or inthe vicinity of a refrigeration or air conditioning apparatus, saidprocess comprising: providing a composition of claim 8 into saidapparatus, and providing a suitable means for detecting said compositionat a leak point or in the vicinity of said apparatus.
 12. A method as inclaim 5 wherein the refrigerant composition further comprises at leastone ultra-violet fluorescent dye selected from the group consisting ofnaphthalimides, perylenes, coumarins, anthracenes, phenanthracenes,xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives ofsaid dye and combinations thereof.
 13. A method as in claim 6 whereinthe heat transfer composition further comprises at least oneultra-violet fluorescent dye selected from the group consisting ofnaphthalimides, perylenes, coumarins, anthracenes, phenanthracenes,xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives ofsaid dye and combinations thereof.
 14. A method as in claim 12, whereinthe refrigerant composition further comprises at least one solubilizingagent selected from the group consisting of hydrocarbons, dimethylether,polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons,esters, lactones, aryl ethers, hydrofluoroethers, and1,1,1-trifluoroalkanes; and wherein the refrigerant and solubilizingagent are not the same compound.
 15. A method as in claim 14 wherein therefrigerant composition is introduced into a compression refrigerationor air conditioning apparatus by (i) dissolving the ultravioletfluorescent dye in the refrigerant composition or heat transfer fluid inthe presence of the solubilizing agent, and introducing the combinationinto said compression refrigeration or air conditioning apparatus or(ii), combining solubilizing agent and UV fluorescent dye andintroducing said combination into said compression refrigeration or airconditioning apparatus containing refrigerant and/or heat transferfluid.
 16. The composition of claim 1 further comprising a stabilizer,water scavenger, or odor masking agent.
 17. The composition of claim 16wherein said stabilizer is selected from the group consisting ofnitromethane, hindered phenols, hydroxylamines, thiols, phosphites andlactones.
 18. The composition of claim 16 wherein said water scavengeris an ortho ester.